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氨基甲酸酯丙烯酸酯单体的合成及其性能研究
Synthesis and Polymerization of Urethane Acrylate Monomers
【作者】 李振风;
【导师】 聂俊;
【作者基本信息】 北京化工大学 , 信息材料, 2008, 硕士
【摘要】 紫外光聚合反应是利用紫外光来引发具有化学反应活性的液态物质快速转变为固态物质的过程,具有固化速度快、污染少、节能和固化产物性能优异等优点。紫外光固化体系一般由低聚物、活性稀释剂、引发剂及其它助剂组成。活性稀释剂又分为单官能团和多官能团活性稀释剂,其中单官能团活性稀释剂由于反应基团浓度低所以反应速率慢。工业常用的氨基甲酸酯丙烯酸酯单体是采用异氰酸酯与醇反应来制备的,由于分子中存在N-H键,分子内及分子间氢键使得单体本身粘度高,导致单体的稀释效率下降。所以本研究论文通过一种非异氰酸酯(NCO)路线合成一类不含N-H键的单官能度氨基甲酸酯丙烯酸酯,测试了单体本身粘度、与树脂混合后的粘度、紫外光聚合动力学、物理机械性能,并与工业常用单官能度单体丙烯酸异冰片酯(IBOA)进行了比较。本论文以吡咯烷、哌啶、吗啡啉、碳酸乙烯酯及丙烯酰氯为主要原料,通过两步反应合成了三种单官能度氨基甲酸酯丙烯酸酯单体。使用傅立叶红外光谱仪和核磁共振仪对相应产物进行了表征;同时使用实时傅立叶变换红外光谱仪(RT-FTIR)对其进行了光聚合动力学研究。结果表明,所合成的三种单体的粘度、与树脂混合后的粘度均比工业常用单体IBOA低。紫外光聚合动力学表明光强、引发剂浓度及引发剂种类对单体的光聚合动力学有较大影响。DMA测试表明本实验所合成的氨基甲酸酯丙烯酸酯单体与树脂混合体系固化后产物的储能模量、Tg比IBOA体系的低。
【Abstract】 Photocuring technology was a process that transformed a reactive liquid into a solid polymer by radiation.Photopolymerization offers multiple advantages including quick curing,environmental friendly, energy saving,good performances of the curing polymer.A UV-curable resin system is generally composed of oligomer,monomer,photoinitiator, and various additives.Reactive diluents are divided to monofunctional monomers and multifunctional monomers.For the low reactive functional group concentration,the monofunctional monomer has low curing rate.In the current UV industrial processes,urethane(meth)acrylates are made through the reaction of isocyanate and polyols.The hydrogen bond of intermolecular and intramolecular makes the viscosity increase and decrease of the diluent-efficiency.In this thesis monofunctional monomers without hydrogen bond were synthesized though a non-NCO route.Three different monofunctional monomers were synthesized by two-step reaction by using pyrrolideine,piperidine,morpholine,ethylene carbonate and acryloyl chloride.Fourier transform infrared spectra(FTIR) and ~1H NMR spectra were used to identify the structures of monomers. The viscosity of monomers and mixtures of monomer/oligomer, photopolymerization kinetics and dynamic mechanical analyzer(DMA) were investigated as well.The synthesized monomers compared with isobornyl acrylate(IBOA).Results showed that the viscosity of monomer and mixture of monomer/oligomer were both lower than that of IBOA. During photopolymerization the light intensity,the concentration of initiator and different kinds of photoinitiator influenced the kinetics parameters.The DMA analysis showed that monomer/CN964(1/4,w/w) had lower Tg and E’ than that of IBOA/CN964(1/4,w/w).
【Key words】 Urethane acrylate monomer; viscosity; diluent efficiency; Kinetics; dynamic mechanical analyzer;
- 【网络出版投稿人】 北京化工大学 【网络出版年期】2008年 11期
- 【分类号】O625.24
- 【下载频次】261